Deodorant formulations and antiperspirant formulations containing particular aliphatic diols and their esters

ABSTRACT

Improved deodorant formulations and antiperspirant formulations are secured by using as an ingredient thereof particular aliphatic diols and their esters.

United States Patent Wright et al. Dec. 23, 1975 DEODORANT FORMULATIONSAND 2,413,803 1/1947 Tribit 424/343 x ANTIPERSPIRANT FORMULATIONS2,496,270 2/1950 Coler 424/343 X Eonnelly..|. i DIOLS AND THEIR ESTERSeray et a 2,627,489 2/1953 Drake et a1. 424/312 x 75 Inventors: DonaldL. Wright, New York, N.Y.; 1 3

- ra enfeld Adam: 2,890,987 6/1959 Hilfer... 424/154 x g 2,900,3068/1959 skim 424/65 [73] Assignee: Exxo Re a h & Engineering 3,222,25212/1965 Kraus 424/312 Li d NJ 3,235,458 2/1966 Messina... 424/683,331,742 7/1967 Babayon 424/312 [22] F11ed: Oct. 28, 1970 3,420,9321/1969 Jones 424/47 [211 App, NOJ 84,931 3,555,145 1/1971 Wetzel et a1.424 47 OTHER PUBLICATIONS 52 us. 01. 424/47; 424/65; 424/66; (ChemicalAbstracts) p- 424/67; 424/68; 424/312; 424/343 v [51] Int. CL A61K 7/32;A61K 7/38; A61K 31/23 Primary Examiner-Donald B. Meyer [58] Field ofSearch 424/65, 68, 312, 343, 47; n y, g r- Heilman; Joseph J 252/522Dvorak [56] References Cited 57 ABSTRACT UNITED STATES PATENTS Improveddeodorant formulations and antiperspirant 1,841,430 1/1932 Bollmann252/522 formulations are secured by using as an ingredient ,3 7/1944Inman 4/3 3 X thereof particular aliphatic diols and their esters.2,404,698 7/1946 Dreyling 424/343 X 2,407,205 9/1946 Wilkes 424/343 4Claims, No Drawings DEODORANT FORMULATIONS AND ANTIPERSPIRANTFORMULATIONS CONTAINING PARTICULAR ALIPHATIC DIOLS AND THEIR ESTERS Thepresent invention is concerned generally with high quality deodorantformulations and antiperspirant formulations which contain as aningredient thereof particular aliphatic diols and their esters. Theformulations of the present invention are particularly desirable sincethey combine effectiveness with desirable physical properties and lackof human toxicity.

During the past decade, considerable progress has been made in thedevelopment of improved deodorant formulations and antiperspirantformulations. These formulations are designed to counteract thedisagreeable effects which result from the perspiration exuded from theglands of the body, such as from the eccrine glands and the apocrineglands, which glands have been estimated to exceed 2,000,000. Forexample, the apocrine gland secretion comprises lipids and proteinaceousmatter which are attacked by bacteria, causing decomposition resultingin malodors. Generally, the bacterial flora of the skin comprisesmicrococci. In general, three approaches have been taken to control bodyodors. One is to utilize antibacterial agents to arrest or preventbacterial decomposition of perspiration by inhibiting bacterial growth.A second approach is the use of a suitable astringent to reduce the flowof perspiration. A third technique that has been suggested is theadministration of anticholinergic compounds to reduce the flow ofperspiration.

It has now been discovered that high quality and very effectivedeodorant and antiperspirant formulations can be prepared by utilizingas an ingredient of said formulation a particular aliphatic diol. Thesealiphatic diols and their esters, when used in deodorant andantiperspirant formulations, will function to destroy the bacteria whichare harmful to the human body. These aliphatic diols, such as aliphatic1,3-diols of 5 to carbon atoms are nontoxic compounds and are veryexcellent when utilized as formulations which come into contact with thehuman body as deodorants and as antiperspirants. These formulations arefar superior over current formulations not only because of their greateffectiveness, but also because they are very safe to use.

The linear 1,3-diols contain from 5 to 15 carbon atoms in the diolportion of the molecule, preferably about 7 to about 10 carbon atoms inthe molecule. The ester portions of the molecule contain from 2 tocarbon atoms, preferably from about 3 to 10 carbon atoms. If a diolester be used, then the number of carbon atoms in the diol chain is from4 to 15. The polyols of the present invention contain hydroxy groupsand/or ester groups on at least the first and third carbon atoms of themolecule. It is this 1,3-dihydroxy configuration which renders thesecompounds very useful as additives because of their inherent safety.Polyalcohols with hydroxyl or ester groups in other positions on thecarbon chain are toxic and, therefore, are not useful as additives. Inaddition to being nontoxic, the 1,3-diols and esters claimed herein havecertain other advantages, making them highly desirable as additives: (1)they are stable, nonvolatile oils and have a long storage and shelflife; (2 they have an appreciable water solubility and are readilyemulsified, making them easy to formulate in various preparations.

A summary of the compounds specifically claimed in this invention, alongwith some of their physical properties, is presented in Tables I and II.This invention is not limited to these specific compounds. Any 1,3-diolcontaining 5 to 15 carbon atoms or its monoor diester is useful for oneor more applications as additives for antiperspirant formulations anddeodorant formulations. Diol esters which contain 4 carbon atoms in thediol chain are also satisfactory.

TABLE I Taste. Diol BP/mm (C) Odor. etc.

Colorless. sweet odor. bitter taste Colorless. slight musty odor, bittertaste Colorless. slight musty odor. slight bitter taste Colorless.slight musty odor. slight bitter taste Colorless, slight musty odor.slight bitter taste Colorless, slight musty odor. slight bitter tasteColorless, slight musty odor, slight bitter taste l,3-pentanediol 78-8l/0.5

1,3-hexanediol 8 l-82/0.2

1,3-heptanediol /05 1,3-0ctanediol 8789/0.3

1.3-nonanediol 126/ l .l

l,3-decanediol mp=30-3l "'mp melting point.

The best esters are those with 5 to 8 carbon hydrocarbon tail in eitherthe diol or ester portion of the compound combined with a concentrationof polar groups in another part of the molecule, as for example,1,3-octanedioll -monopropionate or 1 ,3-butanedioll monooctanoate. Someespecially valuable esters are shown in the following Table II.

MP melting point.

In Table III are summarized the results of toxicity measurements. Thesestudies were conducted with rats.

TABLE II] TOXICITY DATA FOR VARIOUS DlOLS Oral LD Compounds Polyols (7Days) 1 1.3-Pentanediol 20 g/kg 2 1.5-Pentanediol 2 g/kg 31.3-Hexanediol 20 g/kg 4 1.5-Hexanediol 20 g/kg 5 2.5-Hexanediol 2 g/kg6 1.6-Hexanediol 5 g/kg 7 1.3-Heptanediol 20 g/kg 8 1,3-Octanedio1 20g/kg 9 1.3-Nonanediol 20 g/kg 10 1,3-Decanediol g/kg l1 1.3-Undccanediol20 g/kg "'Single dose in rats.

"-"LD lethal dose for 507! kill.

LD values are a common measure of the toxicity of a compound. These LDvalues represent the lethal dose for a 50% kill of the animals testedper unit weight of the animals. The higher the LD value. the lower thetoxicity. The data in Table lll establish that the 1.3-configurations ofpolyalcohols are nontoxic.

It is apparent from the above data that the positioning of the hydroxylgroups has a very significant effect on the toxicity of these compounds.Having hydroxyl groups on the first and third carbon atoms of the chainis sufficient to reduce the toxicity and render the compounds completelysafe for products to be used in contact with the human body and to bestored with complete safety. Thus, there exists no danger of theseproducts causing harm by accidental use either by adults or by children.

The diols of the present invention may be prepared by any suitabletechnique such as by the Reformatsky reaction followed by reduction, orby means of the Prins reaction of formaldehyde and the appropriateolefin. The esters of said diols are prepared by treating the diols withan appropriate acid derivative, such as the free acid, acid chloride oracid anhydride.

The amount of diol and diol ester used may vary widely, depending uponthe particular diol or diol ester employed. Generally, about 2.0% toabout 40.0% by weight of the diol or diol ester is used, based on thetotal composition. If the diol be a lower member such as1,3-pentanediol, it is preferred to use about 2.0% to 10% by weight,preferably 3.0% to 6.0% by weight based on the total composition.

In order to further illustrate the invention, various formulationscontaining an aliphatic 1,3-diol or 1,3- diol ester as an ingredient areas follows:

Note 1,3-pentanediol may be substituted for 1,3- butanediolmonooctanoate. A very desirable formulation is one where a mixture of1,3-butanediol monooc- 4 tanoate and 1,3-pentanediol is used, such as 6%by weight of each.

Formulation 2 Roll-On Antiperspirant Lotion 7: by Weight Range Wax 7.55-10 Water 55.0 40-70 Chlorohydrol 50% wt/wt 31.0 10-40 1.3-Octanemonopropionate* 7.5 5-10 100.0 *Replaces Amount lsopropyl myristate 2.5Butylene glycol 5.0 7.5

Formulation 3 Deodorant Lotion 7: by Weight Range Ethanol 70.0 60-90Carbitol 4.0 1.0-8.0 Perfume 1.0 0.1-3.0 Water 8.0 2.0-14.01,3-Heptanedio1* 17.0 10-20 100.0 *Replaces Amount Ethanol 14.5Propylene glycol 2.0 Hexachlorophene 0.5 17.0

Formulation 4 Deodorant Stick 7: by Weight Range Stearic acid 5.0 2-7Sodium hydroxide 0.8 (1.1-1.5 Triisopropanolamine myristate 0.9 0.5-3.0Ethanol 65.0 10-40 Carbitol 2.0 0.5-4.0 Water 7.0 2-10 Perfume 1.00.5-3.0 1,3-Octanediol* 18.3 10-20 100.0 *Replaces Amount Ethanol 15.0Hexachlorophene 0.3 Glycerine 3.0 18.3

Formulation 5 Spray Deodorant 7: by Weight Range Acetulan 2.0 l-3Perfume 2.0 1-4 Anhydrous ethanol 76.0 60-80 Mixture.*

1.3-Butanedio1 monooctanoate 10.0 5-15 1.3-Heptanediol 10.0 5-15 100.0*Replaces Amount Dipropylene glycol 20.0

Formulation 6 Antiperspirant Lotions for Roll-On Containers by WeightRange Hydroxyethyl ether of cellulose 0.5 0.1-1 .0 Aluminumchlorhydroxide (50% sol.) 40.0 30-60 -continued Formulation 6Antlpersptrant Lotions for Roll-n Containers -'continued Formulation 9.Antlperspirant Cream 3% by Weight 1 Ra ge z y a by Weight Range Water44.5 30-60 5 Water 15.0 l,3-Pentanediol* 10-20 100.0 *Replaces 1 AmountGlycerol monostearate I 2.0. Formulation 1 waer [Q Deodorant Powder l5.0'7( by Weight Range Talc 45.0 30-60 Aluminum chlorhydroxide 30.0 10-40Boric acid 5.0 l-l0 l,3-Decanediol* 20.0 10-20 Formulation 7 g IAntiperspirant m by h Range *Repiaces Amount Methyl cellulose l.00.5-3.0 Kaoline Aluminum chlorhydroxide (50% sol.) 39.0 -50 Perfume 0.30.0l-l.0 Water 39.7 30-50 l.3-Pentanediol* 5.0 1-10 20 That the diols ofthe present invention are very effec- Lloctanedml mompropmate tiveagainst microorganisms is illustrated by the data W listed in Table IV.

TABLE IV Minimum Effective Concentration Against A. P. Ps. S.Debaromyees Compound niger roquefortii aeruginosa typhimurium Sp.

1.3-Heptanediol 0.1% 0.05% 0.2% 1.0% 0.2% 1,3-Butanediol- 0.05% 0.05% XX0.1% 0.2% l-monooctanoate 1,3-Octanediol- 0.05% 0.05% xx 0.1% 1.0%i-monopropionate XX: Not effective at highest level tested. 1%.

The diol and diol esters of the present invention, in addition topreventing growth of odor-producing bac- Replaces Amount teria, haveadditional advantages when used in deodor- Gl cerine 3.0 E y] alcohol 70ants and antipersplrants. The present add tives function water 0 toprevent surface drying and crystallization of creams. 20.0 40 Theyprovide lubricity for roll-on formulations and function to stabilize theoil-in-water emulsions of creams and lotions. in addition, they act asemollients which is especially important and desirable when alu-Formulation 8 minum salts are used. Amipefsplfalion b w ht R Thus, thepresent invention is concerned with the use y ange of particular diolsin deodorant formulations and in Et n h h d l H 288 28-28 antiperspirantformulations. The deodorant formulaifig ig g gft e M a e tions containantibacterial substances which are non- LB-Pentanediol" 5.0 3-7 toxicand which do not cause skin irritations. Also, the m0 0 antibacterialsubstances should not act excessively with *RePlaces Amum respect todecreasing random bacterial flora since that Sodiumsteame 6.0 wouldweaken the defensive mechanism of the skin Sorbitol 3- againstpathogenic organisms. g ig'gg 2:2 Antibacterial substances generallyused are, for ex- 14.0 ample, hexachlorophene, tetramethyl thiuramdisulfide, quaternary ammonium compounds such as 8- hydroxy quinolineand 3,4,4-trichlorocar-banilide. Other antibacterial substances used indeodorants are Formulation 9 di aphene (mii tture of bromosalicylanilides), neomycin, Antiperspirant Cream bithlonoi (ablsphenol), and 1en=exehange resins. Metal by s Range chelates of1,3=diketones lisvln the formula Stearic Acid u i-go R-GQCH 'C0-R areused. Partleular y desirable com- Beeswax 1 Mineral Oil "0 eungs are thecopper, aluminum and ma nesium earn Aluminum chlorhydroxide 22.0 15-30 PI I I a e I t The anuperspirants generally eentam aluminum salts, zinccompounds and zirconium salts. Very satis= 100.0 factory compounds arealuminum ehlorhydroxlde and Replaces Amount aluminumehiorhydrexide/lsetate complex. Aluminum 7 sulfocarbolate and aluminumchlorhydroxy allantoinate compounds are also very satisfactory. Otheraluminum antiperspirant ingredients are aluminum chloride and aluminumsulfate. A very desirable compound is the aluminum sulfamate Al(OH).,(SO NH What is claimed is:

1. In an antiperspirant and deodorant composition containing from about5 to 30% by weight of an astrin gent wherein the improvement comprisesfrom about 2% by weight to about 20% by weight ofa antibacterialcompound selected from the group consisting of esters of saturatednormal aliphatic 1,3-diols with monocarboxylic acids of saturated normalaliphatic hydrocarbons said esters having 4 to carbon atoms in the diolportion of the molecule and 2 to carbon atoms in the acyl portion of themolecule.

2. An antiperspirant cream which comprises by weight of from about 5 to20% of glycerol monostearate, 1 to 5% of spermacetti, about 20% to 60%of water, about 5% to 35% of aluminum sulfate, about 2% to 10% of urea,and about 5% to 40% of an ester of a saturated normal aliphatic1,3-diol, said ester characterized by having 4 to 15 carbon atoms in thediol portion of the molecule and 2 to 20 carbon atoms in the acylportion of the molecule, said acyl portion of the molecule being derivedfrom a monocarboxylic acid of a saturated normal aliphatic hydrocarbon.

3. Formulation as defined by claim 2 wherein said diol isl,3-butanediol-l-monooctanoate.

4. Deodorant lotion which comprises by weight about 60% to of ethanol,about 2% to 14% of water and from about [0% to about 20% of an ester ofasaturated normal aliphatic 1,3-diol with a monocarboxylic acid of anormal saturated aliphatic hydrocarbon, said ester characterized byhaving 4 to 15 carbon atoms in the diol portion of the molecule and 2 to20 carbon atoms in the acyl portion of the molecule.

1. IN AN ANTIPERSPIRANT AND DEODORANT COMPOSITION CONTAINING FROM ABOUT 5 TO 30% BY WEIGHT OF AN ASTRINGENT WHEREIN THE IMPROVEMENT COMPRISES FROM ABOUT 2% BY WEIGHT TO ABOUT 20% BY WEIGHT OF A ANTIBACTERIAL COMPOUND SELECTED FROM THE GROUP CONSISTING OF ESTERS OF SATURATED NORMAL ALIPHATIC 1,3DIOLS WITH MONOCARBOXYLIC ACIDS OF STURATED NORMAL ALIPHATIC HYDROCARBON SAID ESTERS HAVING 4 TO 15 CARBON ATOMS IN THE DIOL PORTION OF THE MOLECULE AND 2 TO 20 CARBON ATOMS IN THE ACYL PORTION OF THE MOLECULE.
 2. An antiperspirant cream which comprises by weight of from about 5 to 20% of glycerol monostearate, 1 to 5% of spermacetti, about 20% to 60% of water, about 5% to 35% of aluminum sulfate, about 2% to 10% of urea, and about 5% to 40% of an ester of a saturated normal aliphatic 1,3-diol, said ester characterized by having 4 to 15 carbon atoms in the diol portion of the molecule and 2 to 20 carbon atoms in the acyl portion of the molecule, said acyl portion of the molecule being derived from a monocarboxylic acid of a saturated normal aliphatic hydrocarbon.
 3. Formulation as defined by claim 2 wherein said diol is 1,3-butanediol-1-monooctanoate.
 4. Deodorant lotion which comprises by weight about 60% to 90% of ethanol, about 2% to 14% of water and from about 10% to about 20% of an ester of a saturated normal aliphatic 1,3-diol with a monocarboxylic acid of a normal saturated aliphatic hydrocarbon, said ester characterized by having 4 to 15 carbon atoms in the diol portion of the molecule and 2 to 20 carbon atoms in the acyl portion of the molecule. 